Self heating cosmetic

ABSTRACT

A packaged self-heating cosmetic, such as a shaving cream, includes separate thermogenically reactive thio-di-alkanol or thio-di-lower alkoxy alkanol reductant and an oxidant, which converts the reductant to the corresponding sulfoxide or sulfone, which serves as a nonionic surface-active or solubilizing constituent of the heated cosmetic. Means are provided for dispensing the packaged reductant and oxidant from separate zones and mixing them together so that they react and heat pressurized shaving cream or other cosmetic product constituents with which the thermogenic reaction mixture is contacted. The reducing agent employed is preferably 2,2&#39;&#39;-thiodiethanol or thiodiethoxyethanol and the oxidizing agent is aqueous hydrogen peroxide.

Elite States Patent 1191 Kenkare et al.

[54] SELF-HEATING COSMETIC [75] Inventors: Divaker B. Kenkare, NorthPlainfield', Durland K. Shumway, Piscataway, both of NJ,

[73] As'signee: Colgate-Palmolive Company,. New

York, N.Y.

22 Filed: Oct.20,1969 21 Appl.No.: 867,897

52 U.S. c1. ..222/14 s, 424/45, 424/47, 424/73,252/s9 51 Int. Cl..........B67d 5/60, A61k 7/14, A61k 7/00 Sawaki, Chem. Abst. Vol.66(1967) page 94502c.

1 1 Mar. 27, 1973 Primary Examiner-Sam Rosen Attorney-Herbert S.Sylvester, Murray M. Grill, Norman Blumenkopf, Ronald S. Cornell, ThomasJ. Corum, Richard N. Miller and Robert L. Stone [57] ABSTRACT A packagedself-heating cosmetic, such as a shaving.

cream, includes separate thermogenically reactive thio-di-alkanol orthio-di-lower alkoxy alkanol reductant and an oxidant, which convertsthe reductant to the corresponding sulfoxide or sulfone, which serves asa nonionic surface-active or solubilizing constituent of the heatedcosmetic. Means are provided for dispensing the packaged reductant andoxidant from separate zones and mixing them together so that they reactand heat pressurized shaving cream or other cosmetic productconstituents with which the thermogenic reaction mixture is contacted.The reducing agent employed is preferably 2,2'-thiodiethanol orthiodiethoxyethanol and the oxidizing agent is aqueous hydrogenperoxide.

9 Claims, No Drawings SELF-HEATING COSMETIC Shaving creams and variousother cosmetics have been known to be more effective and more pleasantto use when employed in a warm or hot condition than when applied atroom temperature. In the past, such products had been heated or the bodysurface on which they were to be applied had been warmed by washing withwarm water. Among the mechanisms used for generating heated foams,especially in the case of shaving creams, were electric machinescontaining agitators and resistance heaters. However, recently, with theadvent of pressurized foam shaving creams, devices for heating the creamafter it is dispensed from the pressurized container have been produced.Some of these utilizeheat transfer between the cream and hot water andothers utilize electrical heating in the dispensing spout. Still otherdevices operate by heating the entire can of pressurized material beforedispensing so that the product dispensed, although it loses some heat byvaporization, will be warm.

Although mechanical and electrical means for heating cosmetics, andshaving creams in particular,'have met with some measure of success,many of such devices available are expensive, unwieldy or inefficient inoperation. Therefore, researchers have turned to chemical means forheating such products. Despite the difficulties of obtaining chemicalsystems which will be compatible with other cosmetic ingredients, ofsufficient stability and heat-generating powerand that will becosmetically acceptable to the consumer, a few systems have beendiscovered that can be utilized to produce heated cosmetics. Usually,the products will be pressurized or aerosol preparations in which thechemically reactive materials are maintained in separate zones and aredispensed together, with other cosmetic ingredients, to produce a heatedproduct. Various chemical mechanisms may be employed to effect thedesired thermogenic reaction but the most successful of these isoxidation. Other mechanisms include neutralization, hydration,hydrolysis, metathesis or other suitable exothermic chemical reactions.

Although the reactions mentioned are capable of generating heat and willwarm the cosmetic being dispensed, care must be taken to assure that thebyproducts of the reactants are cosmetically acceptable. Thus, manysulfur-containing materials are rnalodorous and destroy the appeal ofthe cosmetic, although they may be functionally effective. Somematerials interact with other constituents of the cosmetic with iuhicl'lthey are brought into contact and either destroy or adversely affect thefunctions of such ingredients. Others are toxic or dermatologicalirritants. Some reactant systems, although compatible and otherwiseacceptable,-have to be employed in such proportions that use thereof isnot practicable. In some instances, the systems do not lend themselvesto use with dispensing apparatuses, which usually comprise separatezones, of which one is two to ten times as large as the other, with thelarger zone including the major cosmetic ingredient. Even if the systemis acceptable, commercially available and of low enough cost to make theuse feasible, the reactants displace cosmetic materials and thereby addweight and volume to the product, without any corresponding cosmeticactivity. In other words, in a given dispenser volume, some cosmeticmaterial must be displaced by the thermogenic reactants, therebydiminishing the quantity of cosmetic that may be contained. For example,in the compositions of the U. S. Pat. No. 3,341,418, the byproducts arenot functionallyuseful and occupy space designed for containing cosmeticto be dispensed.

In accordance with the present invention, there is provided a packagedself-heating cosmetic, such as a shaving cream, which includes separatethermogenically reactive thio-di-alkanol or thio-di-lower alkoxy alkanolreductant and an oxidant, such as an aqueous solution of hydrogenperoxide, which converts the reductant to the corresponding sulfoxide,and sometimes to the sulfone. The product produced is useful as asolubilizing constituent in the heated cosmetic or, in many cases,possesses surface active or detergent properties. In addition, anadvantage of such product is that it is nonionic in nature. In cosmeticcompositions, wherein ionic character may sometimes be indicative ofskin-irritating properties and wherein ionic reactions between cosmeticconstituents are to be avoided, this advantage can be important. Infact, in some cases wherein the cation, e.g., sodium, potassium, is acause of skin irritation, it is desirable to replace it with anitrogen-containing cation, such as an alkanolamine or an amine, e.g.,triethanolamine, dipropylamine. The

use of such heavy weight cations adds additional,

materials to the cosmetic composition over and above those normallydesired and increases the weight of the heat-generating chemicals. Thiscan be avoided and the various advantages of the nonionic solubilizersor surface active agents can be obtained by the use in pressurizedcosmetics of the thermogenic systems of the present invention.

The invention is effected by means of a plural compartment container orother suitable package in which the oxidant and reductant compositionsare stored separately, until the intended time of dispensing, when theyare simultaneously discharged from separate sources or compartments intocontact with each other. At the time of such contact, there are presentthe other cosmetic or shaving cream constituents and the cosmetic isheated to a satisfactorily high temperature, as it is dispensed, orshortly thereafter. In some instances, where the heating proceedssomewhat more slowly, it may take from 5 to 30 seconds for appreciablewarmth to be noted and the temperature of the cosmetic may not reach amaximum until 20 to 60 seconds after initial contact of the oxidant andreductant. P resently preferred formulations reach a maximum temperaturewithin 12 to 18 seconds. Such a heating rate is preferred by manyconsumers. Instead of using a p ural compartment single container, acombination of containers or sources of oxidant, reductant and cosmeticmaterial may be employed, wherein all three of these elements orsuitable mixtures thereof are brought together at approximately the sametime, when dispensed. 1

In preferred embodiments of the invention the reductant is2,2'-thiodiethanol, preferably in a composition with other cosmetic orshaving cream constituents, and the oxidant is an aqueous solution ofhydrogen peroxide, kept separate from the other cosmetic constituentsuntil the time of dispensing. However, other dialkanols and oxidizingagents are also useful and may be preferred in particular circumstances.

The plural compartment dispensers which are employed are well known andare commercially available. In these dispensers, a single containerusually includes a main compartment of a generally cylindrical shapewhich contains liquefied gas and other ingredients, plus a smallercompartment or sac, which is collapsible under the pressure of theliquefied gas, as the contents are dispensed. A valve communicates withthe contents of the compartments by means of dip tubes or suitableconnections and allows simultaneous dispensing of the contents, whenopened. Such valve or plural valves, as the case may be, are actuatableby movement of a spout or other dispensing member. Usually, the contentsof the compartments are led through the spout member, wherein they aremixed, and then are discharged from it in heated form, ready for use. Asuitable dispenser is illustrated in U. S. Pat. No. 3,325,056, whereinthe mixing of the reactive components occurs internally. However, it ispreferred for such mixing to be effected externally of the container,preferably in the spout member. In addition to the integral dispensingcontainer, one may also employ combinations of dispensers, each of whichcontains one of the reactive materials, which combination may be such asthat illustrated in U. S. Pat. No. 3,451,593.

The proportions of oxidant and reductant used will normally be aboutstoichiometric. However, in some circumstances, where it is desired toforce the reaction by employing an excess of one or the other of thereactants, or where it is desired that the final composition be eitherof a reducing or oxidizing character, an excess, such as percent, ofeither oxidant or reductant may be employed. Generally, such excess willbe no more than percent of the stoichiometric quantity, and preferably,in the usual case, approximately stoichiometric proportions will beused. The stoichiometric proportions referred to are with respect toreactions for making either the sulfoxide or sulfone. Thus, the moleratio of hydrogen peroxide to thio-di-alkanol or the correspondingalkoxy alkanol may be from 0.75 to 2.5, depending on whether thesulfoxide or sulfone reaction is to be utilized.

The temperature to which the present cosmetic will be raised is usuallycontrolled by valve design, viscosities of the constituents of theoxidant and reductant compositions, the specific identities of theoxidant and reductant employed, and their proportions. Usually suchtemperature will be from 100 to 160F., preferably from l20 to 150F. andmost preferably from 130 to 145F. Thus, the increase in the temperatureof the cosmetic over room temperature will usually be from to 100F. andmost often will be about 60 to 80F. Although heating to suchtemperatures is effected substantially all of the time, nevertheless,the use of the present invention to dispense the materials at othertemperatures is contemplated, when the situation demands.

The thio-di-alkanols and derivatives thereof which are used as thereducing agents in the preparations of this invention may becharacterized as being of the formula OHRS-R'OH wherein ROH and R'OH,which may be the same or different, are either hydroxyalkyl or loweralkoxy hydroxyalkyl groups including poly-lower alkoxy hydroxyalkyl. Thehydroxyalkyls are generally of two to 20 carbon atoms, and thecorresponding alkoxy hydroxyalkyls are of four to 20 atoms in the chain.Although the hydroxyl groups are considered to be terminal in preferredcompounds, intermediately hydroxylated groups are useful reductants too.The shorter the chain, the more solubilizing activity will normally bepossessed by the sulfoxide or sulfone produced, as well as by thereductant. The longer the chain, the more detersive will be the actionof the products. Still, short chain length materials are preferred inmost cases because of the greater heatgenerating capacities that theypossess. Thus, the lower alkylene and lower alkoxy groups preferred arethose of 2 to 4 carbon atoms and most preferably are of two carbonatoms. Exemplary thereof are: CH CH -CH -CH CH CH(CH )CH CH CH -CH -CHAmong the higher alkanol and lower alkoxy higher alkanol-containingcompounds are 2,2'-thiodi-ndodecanol; 2,2-thiodi-n-stearyl alcohol;2,2'-thiodi-noctanol; 2,2'-thiodioleyl alcohol; 2,2-thiodi-ethoxypropoxy-n-dodecanol; and 2,2-thiodi-(ethoxy) -ndodecanol. Specificexamples of the preferred thiodialkanol and correspondingalkoxy-containing reducing agents wherein the alkanol is of up to fourcarbon atoms and the alkoxy is of up to four carbon atoms, with thechain being of 2 to 11 atoms, include HO CH CH,S-CH CH OH; HO-Cl-l CH(CHS-CH(CH -,)CH,OH; HO(CH,) S(CH,);,- OH; HO(CH S(CH 0H; fro-omen, OCH CHSCH CH OCH CH OH; HO (CH CH O) CH CH SCH CH (CH CH O) a) 2 ]a( 2)2 2)2[OCH,CH(CH --OH; and HOCl-l,Cl-l OCH Cl-l S(CH CH O) CH CH OH.

In addition to the above-recited compounds, when desired, substitutedderivatives thereof may be employed, such as those wherein hydrogenatom(s) of an alkylene group or groups is replaced by a non-interferingradical, such as nitro, amino or hydroxy. Up to three such substituentsmay be present in the molecule of reductant. Halogenated, e.g.,chlorinated and brominated, derivatives should be avoided. In someinstances, where otherwise compatible with the formulations, salts ofthe alcohols may be employed, such as the alkali metal, alkaline earthmetal, ammonium,

amine, e.g., lower alkylamines andalkanolamines, e.g., mono-, di-, andtri-lower alkanolamine salts. Of such salts it is preferred to employthe sodium, potassium, triethanolamine, triisopropanolamine,triethylamine and magnesium salts. However, usually the reductant willbe added to the preparations as an alcohol rather than as a salt.Although not presently preferred in the cosmetic preparations of thisinvention, the 2,2-thiodialkanol reductant may be chemically modified byreaction with two molar proportions of an acid anhydride, such assuccinic anhydride, maleic anhydride or phthalic anhydride, to produce adi-ester-acid. Such product can be changed to the sulfoxide or sulfoneby reaction with oxygen and additionally, in those cases where desired,can be neutralized. Thus, by employing an alkaline oxidizing agent, heatmay be generated by both the oxidation and neutralization reactions.

When reacted with hydrogen peroxide or suitable oxidant, thethiodialkanols (this term also applies to the corresponding alkoxycompounds) generate heat rapidly and efficiently, especially in thepresence of catalysts for the redox reaction. In addition to this,however, the products of the reaction, either the preferred sulfoxide orthe sulfone, may include short chain alcohol or alkoxy alcohol groupswhich are solu-' bilizing in their activity. When the chain of atomsbetween the hydroxyl 'and sulfur is from 2 to '6 in number, thecompounds exert a solubilizing activity, due to their hydrophilicnature. When more than six atoms are in such chain, they assume surfaceactive properties, in addition to their solubilizing functions. When thechain is of 12 to 22 atoms the product is detersive. Thus, the productof the redox reaction serves a useful function in the cosmetic orshaving cream preparation, increasing its degree of homogeneity byhelping to solubilize various constituents thereof. It also improves thewetting effect of the product and may increase detergency. This is donewithout introducing cations into the composition and without increasingthe molecular weight of the reducing agent to an objectionable extent.Of course, by mixing the various long and short chain thiodialkanols ofthis invention or by making different chemical compounds containing boththe longer and shorter chains, properties of the reducing agent may becontrolled so as to be most preferable for the particular formulaemployed.

The thiodialkanols may be made by reaction of hydrogen sulfide and theappropriate alkylene oxides, alkanols or alkoxy alkanols, according to 7known techniques. Alternatively, the thiodialkanols can be reacted withalkylene oxide. These reactions result in the production of noundesirable byproduct. The compounds made, although they contain sulfur,are not objectionably malodorous when converted to the sulfoxide orsulfone and can be employed in cosmetic compositions without destroyingor overpowering sensitive perfumes and other cosmetic constituents.

The oxidizing agent which is reacted with the thiodialkanol orthiodialkoxydialkanol may be any suitable such material which convertsthe sulfide to sulfoxide or sulfone and generates enough heat toincrease appreciably the temperature of the cosmetic being dispensed. Agreat varietyof organic and inorganic oxidizing agents may be employedbut it is preferred to use per-compounds. Of these, the inorganicper-compounds (which term is employed in this specification to describeoxygen-releasing compounds, also referred to as per-oxygen compounds)are preferred, especially those which are converted to innocuous oruseful byproducts. The best of these appears to be hydrogen peroxide,preferably utilized in stabilized aqueous solution. However, otherper-compounds such as sodium peroxide, sodium perborate, potassiumpercarbonate, sodium persulfate, and urea peroxide may also besatisfactorily employed. Such per-compounds are preferably used as theiralkali metal, alkaline earth metal or other metal salts, referred to asper-salts. In addition, materials which release hydrogen peroxide areoxidants useful in the practice of the present invention. Of course,mixtures of these may be utilized to adjust properties or obtain specialeffects. Hydrogen peroxide is a preferred oxidizing agent, usually instabilized aqueous solution, because the byproducts of the oxidationreaction are limited to water, when the oxygen is entirely consumed inconverting the sulfide to sulfoxide or sulfone. Of course, water is anormal and desired constituent of cosmetic compositions, includingshaving cream, and does not add irritating cations or other possiblyinterfering ions to the product.

Similarly, the water and sulfoxide or sulfone, in combination, help tosolubilize cosmetic ingredients and improve the surface activity of thefinal preparation. The sulfoxide or sulfone, not containing anysalt-forming ions, also avoids the possibly irritating andinsolubilizing effects of such materials in cosmetics.

The oxidizing agent used is preferably a separate I aqueous solution,not in contact with the other cosmetic and reducing agent constituentsof the present preparation until the time of dispensing. There are timeswhen the oxidizing agent may be present with some of the cosmeticmaterials but these are not the usual cases. The concentration of theoxidant in water may be varied widely, depending on the particularpreparations involved. However, usually from 3 to 30 percent of theper-compound will be employed. When hydrogen peroxide is used this willbe from 5 to 30 percent and preferably from 8 to 20 percent, with themost usual concentrations being 9 to 15 percent of the hydrogen peroxidein aqueous solution. Use of such higher concentrations aids in keepingcontainer size as small as possible or, stated differently, having amaximum amount of cosmetic contained therein, accompanied by maximumfreedom in formulation. Of

course, present with the hydrogen peroxide solution maybe minorproportions of sequestrants, chelating agents and other stabilizers,such as nitrilotriacetic acid or its'trisodium salt, ethylene diaminetetraacetic acid or a salt thereof, stannic chloride, silicates or otherknown compounds useful to stabilize hydrogen peroxide.

The speed of the redox reaction between the peroxide and the thioalkanolreducing agent is significantly increased by the presence of metalcatalysts. Thus, tungstates, molybdates and uranates, and other saltsand catalytic materials for, such oxidation reactions, which may operateby activating the peroxide, may be used to increase the reactionefficiency of a redox system employing per-compounds, such as hydrogenperoxide, as the oxidant. Usually, the alkali metal or ammonium saltsare used, e.g., ammonium molybdate,

potassium tungstate, or sodium uranate. Because metals that activatehydrogen peroxide systems might also act to convert the hydrogenperoxide to a less stable form, in following the present invention thecatalyst will usually be present in the zone containing thethiodialkanol and will not contact the stabilized peroxide until thethermogenic reaction is to be effected. Although the redox reaction willproceed and heat will be generated without use of a catalyst, for rapidgeneration of heat, in preferred embodiments of the invention, a metalsalt catalyst for the redox reaction will usually be employed. Suchcatalysts are known as those which activate the decomposition orreaction of hydrogen peroxide.

The other components of the cosmetic compositions within the presentinvention are those known to the cosmetic art to impart desiredproperties for particular cosmetic purposes. Most cosmetics and shavingcream preparations include both hydrophilic and lipophilic components,often together with emulsifying or wetting agents to help convert themto a stable uniform emulsion. For example, in a hand cream thelipophilic phase may include lanolin, mineral oil, stearic acid,petrolatum, animal fats, vegetable and petroleum waxes and emollients.The aqueous cosmetic phase may contain water, glycerol, solvents,buffers, depilatories, bleaches, waving agents, astringents,stabilizers, deodorants, antiperspirants, or other acitve materials.Soaps or synthetic organic emulsifiers, surface active agents anddetergents may also be present in the aqueous phase and assist inmaintaining the emulsion form. Of course, some materials, are present inboth phases, the greater proportion usually being found in that phase inwhich the material is most soluble. In some cases, solutions may be usedinstead of emulsions. The material dispensed may be in any of severalphysical forms, including liquid, paste, gel or foam. Foams may becreated by the action of a dissolved pressurized or liquefied gasdispersed throughout the composition. The gas expands the composition asthe pressure on it is released, thereby creating the foam. Preferably,for most cosmetic compositions and especially for shaving creams, astable foam form is employed, although sometimes one which is easilyreduced to a liquid may be preferred.

In shaving preparations, the shaving emulsion dispensed from onecompartment of a pressurized container comprises a major proportion, upto about 95 percent of water, usually 50 to 75 percent, and the rest ofthe material includes soap or other beard softeners, solvents,solubilizers, emulsifying, wetting and conditioning agents. The soap ispreferably a stearic acid soap, made from commercial double or triplepressed stearic acid. However, other higher fatty acid soaps, such asthose of tallow, coconut oil, corn oil, cottonseed oil, animal greasesand other animal fats and vegetable oils may be employed. Usuallyhowever, a major proportion of the soap-forming fatty acid of the soapshould be of 16 to l8 carbon atoms. The cation of the soap is preferablyan alkanolamine, such as triethanolamine, although other tri-, di-, andmono-alkanolamines of one to four carbon atoms per alkyl group areuseful, such as diisopropanolamine. If desired, alkali metal soaps, suchas sodium and potassium soaps may be employed, as may be ammonium andlower alkyl amine soaps. For best results in producing a soap which doesnot irritate the skin after shaving and which is fluid enough so as tobe dispensed entirely from the container, a triethanolamine soap isused. Minor proportions of sodium and potassium soaps may be added tohelp stabilize the lather. When superfatting effects are desired, thefatty acid employed, from which the soap is made, may be only partlyneutralized by the cation of a neutralizing agent, leaving the freefatty acid present to exert its emollient effect upon the skin. Usually,in such cases the free fatty acid will be from 0.5 to 30 percent,preferably 10 to 25 percent of the soap content.

Alkylolamides also have a conditioning effect on the hair and skin, inaddition to their property of stabilizing foams of cosmeticcompositions. lncludcd in the alkylolamide groups are dialkylolamides,such as coconut oil fatty acids diisopropanolamide, lauricmyristicdiethanolamide, and other alkylolamides wherein the acyl groups are of12 to 18 carbon atoms, preferably with 50 percent by weight or morebeing of 12 to 14 carbon atoms. The alkylol groups are preferably of oneto three carbon atoms each. Although desirable in many cosmeticcompositions, often the functions of the alkylolamides may be performedby other ingredients or may be unnecessary, in which cases thealkylolamides may be omitted. Suitable substitutes for them asthickeners for foams are the higher fatty acid monoglyceride sulfonatesat concentrations of0.l to 1.5 percent.

Various suitable emulsifying or surface active agents may be importantingredients of the present products. These include the nonionic, anionicand cationic compounds. Of these materials it is preferred to use thenonionics to the exclusion of anionics and cationics, except of thesoap, and of the nonionics the most preferable group is that of thehigher ethers of lower alkoxylated alkyl phenols and of higher fattyalcohols. These compounds, known commercially as lgepals, a trademark ofGAF Corporation, usually have an alkyl group of six to 10 carbon atomson the phenol ring and the degree of alkoxylation (ethoxylation) is fromone to 50,

preferably of l0 to 40 ethoxy groups per molecule, with the higher fattyalcohol being of 10 to 18 carbon atoms per molecule, usually averagingabout 12 carbon atoms. Other nonionic compounds, such as esters ofhigher fatty acids and ethoxylated alcohols, condensates of groups ofhigher ethylene oxide polymers and higher propylene oxide polymers, andesters of ethoxylated fatty acids and sugar alcohols or'hexitans arerepresentative of the nonionics that may be included in the presentformulation. Among the anionic surface active agents are the higheralkyl sulfates and alkyl sulfonates, the higher alkyl benzenesulfonates, ethoxylated fatty alcohol sulfates, monoglyceride sulfates,higher fatty acid amides of amines, such as sodium lauroyl sarcoside,phosphates corresponding to the abovementioned sulfates, and sulfatesand sulfonates of the mentioned nonionic compounds, where possible.Among the cationic surface active agents may be mentioned the quaternaryammonium and phosphonium compounds, e.g., trimethyl benzyl ammoniumchloride, cetyl trimethyl ammonium bromide and lauryl pyridiniurnchloride, all of which exert antiseptic, as well as surface activity.Other emulsifying and surface active agents are described in CosmeticsScience and Technology, by Edward Sagarin (lnterscience Publishers,1957),

particularly at pages l006l008, 1060-63, 775 and 776. This text alsocontains descriptions of other cosmetic materials, such as variousactive ingredients, solvents, emollients, liquefiable gas propellants,conditioning agents, soaps, fatty materials, etc. i

In self-pressurized aerosol" compositions a liquefied gas, such as lowerhydrocarbon or a lower halogenated hydrocarbon, may be employed to aidin discharging the oxidant and reductant portions of the cosmeticpreparation. Especially when the liquefied gas is emulsified into one orboth ofthe portions of the cosmetic, it will assist in generating a foamas .the liquefied propellant is converted to minute gas bubbles. If itis desired to avoid using hydrocarbons or halogenated hydrocarbons, theymay be-replaced with compressed nitrogen, carbon dioxide, the inertgases or other non-liquefied gas, which provides the force to dischargethe oxidant material. Among the liquefied gas propellants which mayusually be employed are the lower hydrocarbons of three to four carbonatoms, which include 'n-butane, isobutane and propane, preferablyemployed as a mixture of isobutane and propane, preferably 85 to 90parts isobutane and 10 to 15 parts propane. The halogenated hydrocarbonsare preferably those which are at least partially fluorinated, includingmonochlorotrifluoromethane, dichlorodifluoromethane,trichlorotrifluoroethane, dichlorotetrafluoroethane,monochloropentafluoroethane, trichloromonofluoromethane,tetrachlorodifluoroethane, and similar chlorofluorohydrocarbons, havingone to three carbon atoms per molecule. Of course, mixtures of thehalogenated hydrocarbons are also employed, desirably to regulate thepressure developed, solubilizing properties, corrosion prevention,emulsion formation, and so forth. In some instances it may be preferableto utilize completely chlorinated or fluorinated hydrocarbons aspropellants or diluents, e.g., methylene chloride, where they areacceptable.

Cosmetic compositions contain adjuvant materials to make the productaesthetically acceptable or specially appealing. Perfumes, dyes,pigments, emollients, solvents, thickeners, solubilizers, humectants,buffers, antiseptics, foaming agents, preservatives and similarmaterials, generally in minor proportions, usually less than percenteach and preferably less than 2 percent each and most preferably lessthan 1 percent each, with the total thereof being less than 25 percent,preferably less than percent and most preferably less than 5 percent ofthe composition, are often employed.

As emollients or solvents it is preferred to employ polyhydric alcoholsof three to six carbon atoms per molecule, having three to six freehydroxyls per molecule. Exemplary of such compounds are glycerol andsorbitol, although other alcohols such as pentaerythritol, mannitol andother sugar alcohols are also used. Of course lanolin and derivativesthereof may also be present.

The proportions of various other constituents of the presentcompositions are regulated to a large extent by the type of compositionbeing prepared. Usually for cosmetic compositions there will be presentfrom 2 to 50 percent of the active cosmetic ingredient, although more orless may also be employed in special cases. There will also usually beemployed from 5 to 90 percent solvent or dispersion medium and from 1 to50 percent of surface active agent, which group includes soaps. In somecircumstances, as in shaving creams, the active ingredient and thesurface active agent may be the same, since one compound serves bothfunctions. In pressurized compositions, there will usually be presentfrom 3 to 90 percent of liquefied or compressed gas. Of course, thegiven proportions apply to most cosmetics,,but it must be realized thatfor certain compositions proportions outside the given ranges may alsobe acceptable, even preferred.

Pressurized shaving creams of this invention preferably contain from 50to 85 percent water, more preferably 65 to 80 percent, 1 to percent ofsynthetic organic surface active agent, exclusive of that produced bythe redox reaction, preferably 2 to 8 percent thereof, or 8 to 35percent, including such surface active or solubilizing product, and 5 to20 percent soap,

preferably 8 to 15 percent thereof. There may also be present 2 to 20percent of humectant, such as glycerine or sorbitol, which may alsoexerta solvent action in the composition. Of course, when the products of thethermogenic reaction also act as humectants, as they often do, or whenhumectant activity is not considered to be needed, such materials may beomitted. In most compositions minor proportions of foaming agent andperfume, both usually within the range of 0.1 to 5 percent andpreferably, from 0.3 to 1 percent are often utilized. In heated shavingcreams the soap solution will usually include from 5 to 40 percent, andpreferably from 8 to 20 percent of the thiodialkanol reactant (this termapplies to those containing alkoxy groups, too), but the thiodialkanolcompound may also be separately dispensed. Together with thethiodialkanol or separately dispensed will often be present 0.2 to 2percent, preferably 0.3 to 1 percent of molybdate or tungstate catalyst,or other suitable catalyst for the reaction in desirable amount. Thehydrogen peroxide contained in the separate compartment to avoidpremature contact with the reductant will usually be from 2 to 10percent of the weight of the soap solution and will be present as anaqueous solution of from 5 to 30 percent strength.

The hydrogen peroxide solution is usually from 10 to percent of the soapsolution weight and is preferably about 20 to 50 percent thereof.

The pH of shaving preparations is normally regulated to be on thealkaline side and is preferably no higher than 10.5. Thus, it ispreferable to employ compositions having a pH of 7 to 10, and mostpreferably 7.7 to 8.7, although those of pH from 5 to l 1 may also beused, when desired for a particular type of application. The pH may beregulated by use of compatible buffers, such as acid-base, salt-base andacid-salt mixtures, e.g., including borates, phosphates, carbonates,sulfates or silicates, or other acceptable inorganic or organic salts,including salts of alkylolamines. The soap or soaps present in theshaving compositions and the sulfoxides or sulfones produced in thethermogenic reaction may exert buffering effects and the soaps may bethe primary buffers present.

The cosmetic preparations of this invention are made by simple methodsknown to the art. The various constituents of the cosmetic portions ofthe preparations themselves may be combined in the normal manner andthen, depending on the nature of the cosmetic, may be further formulatedwith either the oxidizing agent or the reducing agent employed. If thecosmetic preparation is essentially oxidizing in nature, it willpreferably be combined with the oxidizing agent. The reverse situationis also applicable and in most cases, the cosmetic will have theingredients thereof packed together with the reductant and catalyst,with the oxidant being separately packaged, usually in a differentcompartment of the dispenser. If some of the constituents of thecosmetic are oxidizing and others are reducing by nature, thecomposition may be formulated by such parts and one part may accompanythe heat-generating oxidant and the other may be stored with thereductant. The main consideration is that no unwantedoxidation-reduction should occur due to premature combination of aheat-generating chemical of this invention with a cosmetic ingredient.Of course, if so desired, the oxidizing agent and the thiodialkanol maybe kept separate and not formulated with any other cosmetic component.In such situations, the cosmetic may be separately dispensed from acontainer and only brought into contact with the heat-generatingchemicals upon discharge from the container. In such an arrangement athree-compartment container may be employed or three or other number ofseparate containers may be used in conjunction.

Self-heating cosmetic preparations of this invention include variouscompositions intended for application topically to the human body.Usually these are applied to the skin or hair. They include face creams,body tions, depilatories, tanning agents, antiperspirants, sunscreens,personal deodorants, hair creams, hair lotions, hair gels, shampoos,dyes, bleaches, rinses, shaving creams, makeup preparations, bath oils,facial treatments, astringents, aftershave lotions and many otherrelated preparations. In most of these, nonionic surface active agentsor solutilizers are important or useful constituents, either as wettingagents, emulsifiers or solvent aids. By the method of the presentinvention, such compounds are prepared in the dispensing of the cosmeticduring the heating thereof and are immediately solubilized or dispersedin the cosmetic, partly due to the heat generated in the exothermicreaction which produced them. The heat generated produces small currentsin the cosmetic being dispensed which help to distribute the surfaceactive or solubilizing sulfone or sulfoxide and by distributing itthroughout the composition, the ease of wetting the various areas of thecosmetic preparation and solubilizing constituents is further increased.The heat generated also helps further to solubilize cosmetic preparationingredients and thereby improves homogeneity of the product. Thiscoaction between the surface active agent produced, the heat generatedand the other cosmetic preparation ingredients is a useful result of thepresent invention and helps to avoid poorly dispersed ingredients orproducts of the exothermic reaction. The surface activity of thethermogenic product made also helps to distribute throughout thecosmetic the water and other byproducts of the heating reaction andthereby effects a better and more even heating of the cosmetic. Thus,pockets of undispersed materials in the cosmetic are avoided and finalproduct is uniform.

The use of the present reductant-oxidant system for generating heat incosmetic preparations being dispensed allows the employment ofrelatively small quantities of reductant to generate sufficient heat toraise the temperature of the cosmetic appreciably. Of course, as themolecular weight of the reductant becomes greater, and the heat ofreaction does not increase proportionately, more reductant will have tobe used. Nevertheless, the heat developed will be sufficient tosatisfactorily warm cosmetics, even with the higher molecular weightthiodialkanols. It will be noted from a review of the specification andthe examples which follow that it is preferred to employ approximatelythe stoichiometric quantity of oxidizing agent to react to produce thesulfone from the thiodialkanol. Most of the heat developed is from thereaction which produces the intermediate sulfoxide and in some instancesit will be possible and desirable to stop the oxidation reaction at thisstage. Thus, less peroxide will be needed to generate a given amount ofheat. Although it might be desirable to produce only the sulfoxide,often enough oxidizing agent is employed to make the sulfone, to assurethat all of the thiodialkanol will be converted to sulfoxide and thatall the heat of such reactions will be obtained. If the reaction isstopped at the sulfoxide stage, it may sometimes be desirable to addextra reducing agent to the cosmetic composition so as to raise thetemperature even higher. This will be made possible by the moreefficient use of oxidizing agent, since often the smaller sac or zone ofa dispensing container in which the oxidizing agent is contained is of afixed volume and thereby results inthe oxidizing agent being thelimiting factor with respect to heat generation.

The sulfoxides and sulfones are of acceptable odor and therefore, thereaction is not critical with respect to such degree of completion andacceptability of product from an aesthetic viewpoint. Furthermore, thenonionic materials produced, in addition to performing the usefulfunctions set forth earlier, chemically resemble the nonionic surfaceactive agents which are frequently employed as emulsifiers, wettingagents, solubilizers or detergents in the present cosmetics. Similarly,they bear a resemblance to the anionic materials, insofar as the sulfoneor sulfoxide is concerned, since many anionics are sulfonates orsulfates. The chemical resemblances to other constituents of thecosmetic indicate improved compatibilities with these materials.

The oxidants and reductants are low in corrosivity toward ordinarymaterials of container construction, such as tinplate or steel coatedwith resins commonly used for that purpose. Thus, blockages of valveparts are not encountered, due to corrosion byproducts being releasedinto the cosmetic being dispensed through the valve. In addition to lowcorrosive action, the present oxidants and reductants are remarkablycompatible with normal cosmetic ingredients and do not form undesirableproducts that would adversely affect the cosmetic properties of thepreparations. It is considered to be important in many cases that theproducts of the exothermic reaction are not gaseous, since the presentsystems are thereby made useful for liquids, emulsions and creams, aswell as foams. Of course, by use of propellants, such as liquefiedgases,

emulsions may be dispensed as foams and liquids may be dispensed assprays, when desired. Here again, it is often important that the presentexothermic compositions not change the foaming activity of the liquefiedgases or other foaming agents, so that the foaming obtained can bepre-planned, being dependent on the ingredients of the composition used,without being affected by additional gases produced in the heatingreactions. Thus, except for the expansion of the foam on heating, theordinary proportions of foaming agents or spraying agents may be usedwith the cosmetics. Of course, the heat expansion does increase foamvolume and can help save propellant, to some extent.

The lack of gas production in this reaction is a protective feature ofthe invention because accidental rupturing of a sac containing areactant will not result in gas generation. If it did, the pressurecreated could cause the container to explode. It has been found that thepresent exothermic reaction, even if initiated due to sac leakage, willnot cause such explosion.

Although all the above-mentioned properties are of importance inproducing a satisfactory self-heated cosmetic, a most important propertyis low toxicity of the heat-generating chemicals. The present materialsare low in toxicity and are suitable ingredients for cosmetics. Anothervery important property of cosmetics is an acceptable odor. The presentmaterials are of low odor and are aesthetically acceptable. This isimportant when it is considered that many other sulfurcontaining"reducing agents, such as thiourea, for instance, can be oxidized orotherwise converted to malodorous products, thereby making useless anycosmetic in which such reaction occurs. I

With all the above advantages, the present oxidant and reductant areavailable commercial materials and are comparatively inexpensive. Thereductant costs much less than other comparable" organic materialssuggested for use in exothermic aerosol products. For example, thepresent materials are of approximately half the cost of those suggestedin U. S. Pat No. 3,341,418 and in addition, of course, perform usefulfunctions in the final cosmetic compositions. Such additional utilities,without additional expenses, further diminish the effective costs ofthese'reductants.

The following examples illustrate some preferred compositions within thepresent invention. Of course, such examples are not to be considered aslimiting the invention, because they are only exemplary thereof. Thoseof skill in the art will know how to replace various constituents andprocedural steps of the invention with corresponding equivalentmaterials or operations without departing from the principles orteachings imparted herein. Unless otherwise stated, all parts are givenby weight.

EXAM PLE 1 Parts Stearic acid (double pressed) 10.5 Nonyl phenylpolyoxyethylene ethanol of 5.0 30 oxyethylene groups per mole (lgepalCO-880) Laurie myristic diethanolamide 0.5 Trithanolamine 5 .0 Water(deionized) 64.3 2,2'-thiodiethanol 10.0 Sodium tungstate aqueoussolution) 4.0 Perfume 0.7

The stearic acid, lauric myristic diethanolamide and nonyl phenylpolyoxyethylene ethanol are mixed together and heated to 185F. Thetriethanolamine and water are combined and heated to the sametemperature and both portions at 185F. are combined. The emulsionproduced is cooled to F. and the perfume, 2,2'-thiodiethanol and sodiumtungstatesolution are added and the product is cooled further to 80F.This portion of the cosmetic preparation is then added to the largercompartment of a plural compartment dispensing container. Next, 25 partsof a 14 percent hydrogen peroxide solution (aqueous) are filled into thesmaller compartment of the dispenser, which is a plastic sac. Both thelarger and smaller compartments communicate with a dispensing valve orvalves. Such valve is then staked into place at the outlet of thedispensing container and 40.0 parts of liquefied gas propellant arepressure filled into the larger compartment, to desired operatingpressure (about 40 lbs./sq. in.). Of course, the gas exerts pressure onthe contents of both compartments. The hydrocarbon propellant employedis a mixture of 83.5 percent isobutane and 16.5 percent propane.Immediately after manufacture is completed, the pressurized thermogenicshaving cream is ready for use.

The thermogenic shaving cream made has a good shelf lifeand will notdestroy the perfume or lose heating strength to a significant extentduring reasonable storage. The product is pleasant to use and the heatedcream dispensed when the dispensing spout is depressed and the valveports are opened is an effective softener for the beard and a goodlubricant for the razor. Shaving is almost effortless with this product.The temperature at which the cream is used is l40F., the temperature towhich the cream is raised shortly after dispensing (within 15 seconds).The cream is pleasantly perfumed and the lime perfume odor is notaffected by any malodor. The lather produced is of excellent stabilityand is superior in this respect to previously known hot lather aerosolshaving creams.

Similar results are obtained when the amounts of oxidant and reductantare increased and decreased, within a 25 percent variation, buttemperature variations are noted. Thus, when the hydrogen peroxide isdecreased to 20 parts and the thiodiethanol is decreased to 8 parts thetemperature of the shaving cream is raised only to about F., whereaswhen the amounts are increased to 30 and I2 parts, respectively, thecream is heated to over F. When the ratios of oxidant to reductant arechanged, by up to 25 percent, with the weight of one material beingapproximately that of this example, heating is improved when the effectis to add reactant and is worsened when the opposite result is attained.Concentrations of the oxidant can be changed from 8 to 20 percent inwater, without affecting the heat generated, if the amount of hydrogenperoxide remains substantially constant. When other oxygen-releasingmaterials such as urea hydrogen peroxide, sodium perborate, potassiumpersulfate and other per-compounds are employed instead of the hydrogenperoxide, in aqueous solution, the reaction also goes and the shavingcream dispensed is heated to approximately the temperature hereinobtained, providing that stoichiometric replacement proportions arepresent. Such comparable effects are also obtained when the2,2'-thiodialkanol is replaced with an equivalent heatgenerating amountof the other thiodialkanols, including those which are alkoxylated. Withthe more highly alk-oxylated and longer chain alkanols the product ofthe thermogenic reaction also adds surface active and detersive as wellas solubilizing activities to the cosmetic produced.

In the absence of a catalyst for the redox reaction the heating issomewhat slower but is still useful for cosmetic purposes. Of course,when the sodium tung- I state is replaced by the equivalent amount ofammonium molybdate, potassium uranate or other redox catalyst suitablefor use in the present cosmetics, the development of heat is acceleratedand is comparable to the action noted in the preparation of thisexample.

EXAMPLE 2 Stearic acid 13.0

Nonyl phenyl polyoxyethylene ethanol of 30 polyoxyethylene groups permole Lauric myristic diethanolamide Triethanolamine Water 92,2'-thiodiethanol 1 Sodium tungstate (10% aqueous solution) PerfumeHydrogen peroxide (10% aqueous solution) Propellant (5:1isobutanepropane mixture) This formula is prepared in the same manner asdescribed previously in Example 1. The product resulting hasapproximately the same properties except for the temperature generatedby the thermogenic reaction being lower, approximately at l30-l 35F. Theshaving cream is effective in wetting the beard and softening the hairsthereof. It is as stable as the cream of Example 1 and is satisfactorilyshelf stable.

When, instead of the shaving cream base of the present example, there isused with the oxidant-reductant combination, catalyst and propellantanother cosmetic base, such as a shampoo, depilatory, facial cleanser,sun-screening preparation, skin or hair conditioner, sunburn cream hairdye or other colorant, cold cream or another preparation described orsuggested in this specification, a corresponding heated product results,with the temperature thereof being from 120 to 150F. Of course, in theappropriate formulations there may be added various other ingredients,in addition to the active agents, such as thickeners, anti-foam agents,foaming agents, detergents, stabilizers, etc., as will be known to thoseof skill in the art. The product may be dispensed as foams or as sprays,readily breaking foams, liquids, pastes or dispersions. Combinationproducts may be obtained by mixing such compositions. Such products areall compositions within the ambit of the present disclosure and theseexamples.

EXAMPLE 3 Parts Stearic acid 12.0 Nonyl phenyl polyoxyalkylcne alkanol5.0 (30 oxyethylene groups, ethanol) Sodium lauroyl monoglyceridesulfonate 1.0 (Siponate SGS) Triethsnolamine 6.0 Water (deionized) 62.02,2-thiodiethanol 13.0 Sodium tungstate 0.25 Perfume 0.75

The above formula is compounded in a manner like that employed to makethe composition of Example 1. The monoglyceride sulfonate is added inplace of the lauric myristic dialkanolamide. 30 percent more hydrogenperoxide is used, since more reductant is also employed. The productresulting is a good self-heating shaving cream, the temperature of whichincreases to about 150F. within 18 seconds after dispensing.

The foam of this shaving cream is thick and stable, such propertiesbeing contributed to by the monoglyceride sulfonate. When 0.5 percent orless of the sulfonate is used the foam becomes appreciably thinner. At1.5 percent content a very thick foam results. Usually, no more than 1.5percent of the monoglyceride sulfonate will be employed to avoidoverthickening. Also the cation may be changed to other alkali metal,alkaline earth metal, ammonium, alkylamine or lower alkanolamine saltand similar results are obtained, if the acyl group is of 10 to 18carbon atoms.

When the stearic acid and triethanolamine content are cut to 10 and 5percent, respectively, and the monoglyceride sulfonate is omitted, withwater content adjusted to 66 percent, a thinner but usable foam results.

EXAMPLE 4 Parts Stearic acid 10.0 Nonyl phenyl polyoxyethylene ethanolof 5.0 30 oxyethylene groups per mole Aqueous sorbitol solution (70%sorbitol) 10.0 Triethanolamine 5.30 Water (deionized) 52.952,2'-thiodiethanol 14.0 Sodium tungstate (25% aqueous solution) 2.0Perfume 0.75

The various ingredientsare combined, as described in Example 1, with theexception that sorbitol solution is added after neutralization of thestearic acid by the triethanolamine. 144 parts of the composition arethen added to the larger compartment of a two compartment dispenser.Following this, 36 parts ofa 14 percent hydrogen peroxide aqueoussolution are added to the smaller compartment of the dispenser. Bothcompartments communicate with a dispensing valve, which is staked intoplace at the top of the dispenser and is actuatable by finger pressure.Next, six parts of hydrocarbon propellant (5/6 isobutane and H6 propane)are back-filled by pressure into the larger compartment. The product isnow ready for use.

As was mentioned with respect to the other shaving creams of thisinvention, this product has good shelf life and does 'not destroy thepleasant aroma of its' perfume on standing. Neither does it lose heatingpower on reasonable storage. The temperature to which the dispensedproduct is raised by the chemical reaction of the 2,2-thiodiethanol andthe hydrogen peroxide is over F. and this temperature is reached shortlyafter dispensing, usually within 12 to 18 seconds. No objectionablemalodor is noted, after dispensing. The lather produced is a very stableone and the foam is long lasting and apparently of very finely dividedbubbles. It feels especially pleasant on the skin. The improvedproperties of this lather are considered to be due in part to thepresence of the sorbitol in the formulation. This polyhydric alcoholexerts emollient effects,

as has been mentioned in the specification, and additionally, aids inproducing a highly acceptable rich, stable foam. Similar results areobtained when other polyhydric alcohols, e.g., mannitol, glycerol, areincluded in the formulation.

In other compositions, the proportion of propellant is changed, so thatfrom 2 to 8 parts are used, instead of the six parts shown in thisformula. Acceptable products are obtainable in'this range, althoughthosewith the lesser amounts of propellant are dispensed more slowly and donot possess as fine bubble structure as do those in which morepropellant is employed. Care must be taken to avoid using too little ortoo much propellant to avoid dripping of product or running on the onehand, and sputtering, on the other.

The invention has been describedand illustrated. Of course, it is notlimited to specific examples given but includes various compositions andmethods in which equivalents are employed, providing that such arewithin the spirit of the invention and in accord with the presentteachings.

What is claimed is:

1. A self-heating cosmetic product comprising constituents of a cosmeticcomposition stored in separate zones of a package containing a pluralityof compartments, in one of which there is present an aqueous mediumincluding an organic reductant of the formula HO-R-S-R'-OH, wherein ROHand ROH, which may be the same or different, are selected from the groupconsisting of hydroxyalkyl, lower alkoxy hydroxyalkyl, di-lower alkoxyhydroxyalkyl and poly-lower alkoxy hydroxyalkyl and substitutedderivatives thereof wherein the substituents are selected from the groupconsisting of nitro, amino and hydroxy, which replace alkylene hydrogensand are limited to three per reductant molecule, and salts thereof, thehydroxyalkyls being of twoto carbon atoms and the alkoxy hydroxyalkyls,di-alkoxy hydroxyalkyls and poly-alkoxy hydroxyalkyls being of four to20 atoms in a chain, with the alkoxies being of two to four carbonatoms, and in the other of which compartments there is present anoxidizing agent which is a per-oxygen compound selected from the groupconsisting of hydrogen peroxide, urea peroxide, and .metal per-salts,ther mogenically reactive with the reductant to convert it to a compoundselected from the group consisting of the corresponding sulfoxides andsulfones having surface active or solubilizing effects on thecosmetic-composition ingredients and simultaneously to heat the cosmeticwhen dispensed, and means for dispensing contents from both zones sothat they are brought into contact with each other and cosmeticingredients to produce a heated cosmetic including therein a sulfoxideor sulfone product of the thermogenic reaction.

2. A self-heating cosmetic product according to claim 1 wherein ROH andR'OH are unsubstituted hydroxyalkyls, and the oxidant is hydrogenperoxide or a metal per-oxygen salt.

3. A self-heating cosmetic product according to claim 2 wherein ROH andR'OH are hydroxyethyl, the oxidant is aqueous hydrogen peroxide, theproportion of reductant to oxidant is from 0.9 times the stoichiometricquantity to produce the corresponding sulfoxide to 1.25 times thestoichiometric quantity to produce the corresponding sulfone, and thereis present in the same compartment as the reductant the cosmeticmaterial to be dispensed and a catalyst for the redox reaction, in aneffective proportion and amount to accelerate the thermogenic reactionand heat the cosmetic to a temperature of at least F. within 30 secondsafter dispensing, said catalyst being an alkali metal or ammoniummolybdate, tungstate or uranate.

I 4. A self-heating shaving cream product comprising constituents of ashaving cream composition stored in separate zones of a packagecontaining a plurality of compartments, in one of which is present anaqueous medium including an organic reductant of the formula HO-R-S-R-OHwherein ROH and ROH, which may be the same or different, are selectedfrom the group consisting of hydroxyalkyl, lower alkoxy hydroxyalkyl,-

di-lower alkoxy hydroxyalkyl and poly-lower alkoxy hydroxyalkyl andsubstituted derivatives thereof wherein the substituents are selectedfrom the group consisting of nitro, amino and hydroxy, which replacealkylene hydrogens and are limited to three per reductant molecule, andsalts thereof, the hydroxyalkyls being of two to 20 carbon atoms and thealkoxy hydroxyalkyls, di-alkoxy hydroxyalkyls and poly-alkoxyhydroxyalkyls being of four to 20 atoms in a chain, with the alkoxies'being of two to four carbon atoms, higher fatty acid soap having acation selected from the group consisting of alkanolamines, amines,ammonium, and alkali metal and in which the fatty acids contentcomprises a major proportion of fatty acid(s) of [6 to 18 carbon atoms,and water, and in the other of which compartments there is present anoxidizing agent which is a per-oxygen compound selected from the groupconsisting of hydrogen peroxide, urea peroxide and metal per-salts,thermogenically reactive with the reductant to convert it to a compoundselected from the group consisting of the corresponding sulfoxides andsulfones having surface active or solubilizing effects on the shavingcream composition ingredients and simultaneously to heat the shavingcream when dispensed, and means for dispensing contents from both zonesso that they are brought into contact with each other and the shavingcream ingredients to produce a heated shaving cream including therein asulfoxide or sulfone product of the thermogenic reaction.

5. A self-heating shaving cream product according to claim 4 wherein ROHand R'OH are unsubstituted hydroxyalkyls, the oxidant is hydrogenperoxideor a metal per-oxygen salt and the means for dispensing thecontents of the zones is a liquefied gas under pressure selected fromthe group consisting of lower hydrocarbons, lower halogenatedhydrocarbons and mixtures thereof.

6. A self-heating shaving cream product according to claim 5 wherein ROHand R'OH are hydroxyethyl, the oxidant is aqueous hydrogen peroxide, theproportion of reductant to oxidant is from 0.9 times the stoichiometricquantity to produce the corresponding sulfoxide to 1.25 times thestoichiometric quantity to produce the corresponding sulfone, and thereis present in the same compartment as the reductant, soap and water, acatalyst for the redox reaction, in an effective proportion and amountto accelerate the thermogenic reaction and heat the shaving cream to atemperature of at least lOOfF. within 30 seconds after dispensing, saidcatalyst being an alkali metal or ammonium molybdate, tungstate oruranate.

7. A self-heating shaving cream product according to claim 6 wherein thereductant component comprises from to 40 percent of the composition inthe reductant compartment, the catalyst for the redox reaction comprises0.2 to 2 percent thereof and the soap is triethanolamine soap, and theoxidant component is an aqueous solution of hydrogen peroxide in whichthe active hydrogen peroxide content is from 2 to 10 percent of theweight of the reductant component.

8. A self-heating shaving cream product according to claim 7 wherein theshaving cream dispensed is propelled by a mixture of propane andisobutane, is exothermically heated to a temperature of at least 130F.,

and comprises 50 to percent water, I to 35 percent of a surface activeagent which is a nonionic higher alkylphenyl poly-lower alkoxy loweralkanol, 5 to 20 percent of triethanolamine soap and less than 25percent of adjuvants, with the pH at dispensing being from 7 to 10.

9. A self-heating shaving cream product according to claim 8 whichcomprises about 15 parts of trietha'nolamine stearate, 5 parts of nonylphenyl polyoxyethylene ethanol of 30 oxyethylene groups per mole, 10parts of 2,2'-thiodiethanol, 0.5 part of lauric myristic diethanolamide,0.4 part of sodium tungstate, 3.5 parts of hydrogen peroxide and partsof water, before dispensing.

* III

2. A self-heating cosmetic product according to claim 1 wherein ROH andR''OH are unsubstituted hydroxyalkyls, and the oxidant is hydrogenperoxide or a metal per-oxygen salt.
 3. A self-heating cosmetic productaccording to claim 2 wherein ROH and R''OH are hydroxyethyl, the oxidantis aqueous hydrogen peroxide, the proportion of reductant to oxidant isfrom 0.9 times the stoichiometric quantity to produce the correspondingsulfoxide to 1.25 times the stoichiometric quantity to produce thecorresponding sulfone, and there is present in the same compartment asthe reductant the cosmetic material to be dispensed and a catalyst forthe redox reaction, in an effective proportion and amount to acceleratethe thermogenic reaction and heat the cosmetic to a temperature of atleast 100* F. within 30 seconds after dispensing, said catalyst being analkali metal or ammonium molybdate, tungstate or uranate.
 4. Aself-heating shaving cream product comprising constituents of a shavingcream composition stored in separate zones of a package containing aplurality of compartments, in one of which is present an aqueous mediumincluding an organic reductant of the formula HO-R-S-R''-OH wherein ROHand R''OH, which may be the same or different, are selected from thegroup consisting of hydroxyalkyl, lower alkoxy hydroxyalkyl, di-loweralkoxy hydroxyalkyl and poly-lower alkoxy hydroxyalkyl and substitutedderivatives thereof wherein the substituents are selected from the groupconsisting of nitro, amino and hydroxy, which replace alkylene hydrogensand are limited to three per reductant molecule, and salts thereof, thehydroxyalkyls being of two to 20 carbon atoms and the alkoxyhydroxyalkyls, di-alkoxy hydroxyalkyls and poly-alkoxy hydroxyalkylsbeing of four to 20 atoms in a chain, with the alkoxies being of two tofour carbon atoms, higher fatty acid soap having a cation selected fromthe group consisting of alkanolamines, amines, ammonium, and alkalimetal and in which the fatty acids content comprises a major proportionof fatty acid(s) of 16 to 18 carbon atoms, and water, and in the otherof which compartments there is present an oxidizing agent which is aper-oxygen compound selected from the group consisting of hydrogenperoxide, urea peroxide and metal per-salts, thermogenically reactivewith the reductant to convert it to a compound selected from the groupconsisting of the corresponding sulfoxides and sulfones having surfaceactive or solubilizing effects on the shaving cream compositioningredients and simultaneously to heat the shaving cream when dispensed,and means for dispensing contents from both zones so that they arebrought into contact with each other and the shaving cream ingredientsto produce a heated shaving cream including therein a sulfoxide orsulfone product of the thermogenic reaction.
 5. A self-heating shavingcream product according to claim 4 wherein ROH and R''OH areunsubstituted hydroxyalkyls, the oxidant is hydrogen peroxide or a metalper-oxygen salt and the means for dispensing the contents of the zonesis a liquefied gas under pressure selected from the group consisting oflower hydrocarbons, lower halogenated hydrocarbons and mixtures thereof.6. A self-heating shaving cream product according to claim 5 wherein ROHand R''OH are hydroxyethyl, the oxidant is aqueous hydrogen peroxide,the proportion of reductant to oxidant is from 0.9 times thestoichiometric quantity to produce the corresponding sulfoxide to 1.25times the stoichiometric quantity to produce the corresponding sulfone,and there is present in the same compartment as the reductant, soap andwater, a catalyst for the redox reaction, in an effective proportion andamount to accelerate the thermogenic reaction and heat the shaving creamto a temperature of at least 100* F. within 30 seconds after dispensing,said catalysT being an alkali metal or ammonium molybdate, tungstate oruranate.
 7. A self-heating shaving cream product according to claim 6wherein the reductant component comprises from 5 to 40 percent of thecomposition in the reductant compartment, the catalyst for the redoxreaction comprises 0.2 to 2 percent thereof and the soap istriethanolamine soap, and the oxidant component is an aqueous solutionof hydrogen peroxide in which the active hydrogen peroxide content isfrom 2 to 10 percent of the weight of the reductant component.
 8. Aself-heating shaving cream product according to claim 7 wherein theshaving cream dispensed is propelled by a mixture of propane andisobutane, is exothermically heated to a temperature of at least 130*F., and comprises 50 to 85 percent water, 1 to 35 percent of a surfaceactive agent which is a nonionic higher alkylphenyl poly-lower alkoxylower alkanol, 5 to 20 percent of triethanolamine soap and less than 25percent of adjuvants, with the pH at dispensing being from 7 to
 10. 9. Aself-heating shaving cream product according to claim 8 which comprisesabout 15 parts of triethanolamine stearate, 5 parts of nonyl phenylpolyoxyethylene ethanol of 30 oxyethylene groups per mole, 10 parts of2,2''-thiodiethanol, 0.5 part of lauric myristic diethanolamide, 0.4part of sodium tungstate, 3.5 parts of hydrogen peroxide and 90 parts ofwater, before dispensing.